New! View global litigation for patent families

US20050032302A1 - Methods of forming capacitors - Google Patents

Methods of forming capacitors Download PDF

Info

Publication number
US20050032302A1
US20050032302A1 US10636035 US63603503A US2005032302A1 US 20050032302 A1 US20050032302 A1 US 20050032302A1 US 10636035 US10636035 US 10636035 US 63603503 A US63603503 A US 63603503A US 2005032302 A1 US2005032302 A1 US 2005032302A1
Authority
US
Grant status
Application
Patent type
Prior art keywords
portion
oxide
material
temperature
metal
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
US10636035
Other versions
US6855594B1 (en )
Inventor
Vishwanath Bhat
Chris Carlson
F. Gealy
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Micron Technology Inc
Original Assignee
Micron Technology Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date

Links

Images

Classifications

    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00Fixed capacitors; Processes of their manufacture
    • H01G4/002Details
    • H01G4/018Dielectrics
    • H01G4/06Solid dielectrics
    • H01G4/08Inorganic dielectrics
    • H01G4/085Vapour deposited
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00Fixed capacitors; Processes of their manufacture
    • H01G4/002Details
    • H01G4/018Dielectrics
    • H01G4/06Solid dielectrics
    • H01G4/08Inorganic dielectrics
    • H01G4/12Ceramic dielectrics
    • H01G4/1272Semiconductive ceramic capacitors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00Fixed capacitors; Processes of their manufacture
    • H01G4/33Thin- or thick-film capacitors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers
    • H01L21/314Inorganic layers
    • H01L21/316Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/3165Inorganic layers composed of oxides or glassy oxides or oxide based glass formed by oxidation
    • H01L21/31683Inorganic layers composed of oxides or glassy oxides or oxide based glass formed by oxidation of metallic layers, e.g. Al deposited on the body, e.g. formation of multi-layer insulating structures
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L28/00Passive two-terminal components without a potential-jump or surface barrier for integrated circuits; Details thereof; Multistep manufacturing processes therefor
    • H01L28/40Capacitors
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer, carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers
    • H01L21/314Inorganic layers
    • H01L21/316Inorganic layers composed of oxides or glassy oxides or oxide based glass
    • H01L21/31604Deposition from a gas or vapour
    • H01L21/31616Deposition of Al2O3

Abstract

A method of forming a capacitor includes forming a conductive metal first electrode layer over a substrate, with the conductive metal being oxidizable to a higher degree at and above an oxidation temperature as compared to any degree of oxidation below the oxidation temperature. At least one oxygen containing vapor precursor is fed to the conductive metal first electrode layer below the oxidation temperature under conditions effective to form a first portion oxide material of a capacitor dielectric region over the conductive metal first electrode layer. At least one vapor precursor is fed over the first portion at a temperature above the oxidation temperature effective to form a second portion oxide material of the capacitor dielectric region over the first portion. The oxide material of the first portion and the oxide material of the second portion are common in chemical composition. A conductive second electrode layer is formed over the second portion oxide material of the capacitor dielectric region.

Description

    TECHNICAL FIELD
  • [0001]
    The invention is related to methods of forming capacitors.
  • BACKGROUND OF THE INVENTION
  • [0002]
    A continuing goal in integrated circuitry fabrication is to form the circuitry components to be smaller and denser over a given area of a semiconductor substrate. One common circuit device is a capacitor, which has a capacitor dielectric region received between a pair of conductive electrodes. In such devices, there is a continuous challenge to maintain sufficiently high storage capacitance despite decreasing area in the denser circuits. Additionally, there is a continuing goal to further decrease cell area. One manner of increasing cell capacitance is through cell structure techniques. Such techniques include three-dimensional cell capacitors, such as trench or stacked capacitors.
  • [0003]
    Highly integrated memory devices, for example 256 Mbit DRAMs and beyond, are expected to require a very thin dielectric film for the three-dimensional capacitors of cylindrically stacked, trenched or other structures. To meet this requirement, the capacitor dielectric film thickness will be below 2.5 nanometer of SiO2 equivalent thickness. Accordingly, materials other than SiO2 having higher dielectric constants are expected to be used. Si3N4 is one such material which has been used either alone or in combination with silicon dioxide as a capacitor dielectric region. Insulating inorganic metal oxide materials, for example Al2O3, Ta2O5 and barium strontium titanate, have even higher dielectric constants and low leakage currents which make them attractive as capacitor dielectric materials for high density DRAMs, non-volatile memories and other integrated circuitry.
  • [0004]
    In many of such applications, it will be highly desirable to utilize metal for the capacitor electrodes, thus forming a metal-insulator-metal (MIM) capacitor. In the context of this document, a “metal” encompasses elemental metals, alloys of elemental metals, and metal compounds regardless of stoichiometry. Exemplary conductive metals proposed for use with Al2O3 as the capacitor dielectric material include titanium nitride, tungsten nitride and tantalum nitride. Unfortunately, these materials can be appreciably oxidized when exposed to the typical chemical vapor deposition or atomic layer deposition (ALD) techniques under which Al2O3 (or other dielectric materials) would be deposited. The oxides which form typically have a reduced dielectric constant or increased leakage than Al2O3, thereby having an adverse effect on the capacitor being fabricated. It would be desirable to at least reduce the degree of oxidation of a metal capacitor electrode layer during the formation of an oxide dielectric thereover.
  • [0005]
    While the invention was motivated from this perspective, it is in no way so limited. The invention is only limited by the accompanying claims, appropriately interpreted in accordance with the doctrine of equivalents, without limiting reference to the specification, and with the specification herein only providing but exemplary preferred embodiments.
  • SUMMARY OF THE INVENTION
  • [0006]
    The invention includes methods of forming capacitors. In one implementation, a method of forming a capacitor includes forming a conductive metal first electrode layer over a substrate, with the conductive metal being oxidizable to a higher degree at and above an oxidation temperature as compared to any degree of oxidation below the oxidation temperature. At least one oxygen containing vapor precursor is fed to the conductive metal first electrode layer below the oxidation temperature under conditions effective to form a first portion oxide material of a capacitor dielectric region over the conductive metal first electrode layer. At least one vapor precursor is fed over the first portion at a temperature above the oxidation temperature effective to form a second portion oxide material of the capacitor dielectric region over the first portion. The oxide material of the first portion and the oxide material of the second portion are common in chemical composition. However, the oxide of the second material might be of higher density and have superior electrical properties as compared to the first portion of the oxide material. A conductive second electrode layer is formed over the second portion oxide material of the capacitor dielectric region.
  • [0007]
    In one implementation, a method of forming a capacitor includes forming a conductive metal first electrode layer over a substrate, with the conductive metal first electrode layer being oxidizable to a higher degree at and above an oxidation temperature as compared to any degree of oxidation below the oxidation temperature. A capacitor dielectric region is formed over the conductive metal first electrode layer by atomic layer deposition. The atomic layer deposition comprises forming a first portion of the capacitor dielectric region at a temperature below the oxidation temperature, and forming a second portion of the capacitor dielectric region over the first portion at a temperature above the oxidation temperature. The first portion restricts oxidation of the conductive metal first electrode layer during formation of the second portion. A conductive second electrode layer is formed over the second portion of the capacitor dielectric region.
  • [0008]
    Other aspects and implementations are contemplated.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • [0009]
    Preferred embodiments of the invention are described below with reference to the following accompanying drawings.
  • [0010]
    FIG. 1 is a diagrammatic sectional view of a semiconductor wafer fragment in process in accordance with an aspect of the invention.
  • [0011]
    FIG. 2 is a view of the FIG. 1 wafer fragment at a processing step subsequent to that shown by FIG. 1.
  • [0012]
    FIG. 3 is a view of the FIG. 2 wafer fragment at a processing step subsequent to that shown by FIG. 2.
  • [0013]
    FIG. 4 is a view of the FIG. 3 wafer fragment at a processing step subsequent to that shown by FIG. 3.
  • [0014]
    FIG. 5 is a diagrammatic sectional view of a semiconductor wafer fragment in process in accordance with an aspect of the invention.
  • [0015]
    FIG. 6 is a view of the FIG. 5 wafer fragment at a processing step subsequent to that shown by FIG. 5.
  • [0016]
    FIG. 7 is a view of the FIG. 6 wafer fragment at a processing step subsequent to that shown by FIG. 6.
  • [0017]
    FIG. 8 is a view of the FIG. 7 wafer fragment at a processing step subsequent to that shown by FIG. 7.
  • DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • [0018]
    This disclosure of the invention is submitted in furtherance of the constitutional purposes of the U.S. Patent Laws “to promote the progress of science and useful arts” (Article 1, Section 8).
  • [0019]
    The invention is described in a first preferred embodiment in connection with FIGS. 1-4. FIG. 1 depicts a semiconductor substrate 10 comprising bulk monocrystalline silicon material 12. In the context of this document, the term “semiconductor substrate” or “semiconductive substrate” is defined to mean any construction comprising semiconductive material, including, but not limited to, bulk semiconductive materials such as a semiconductive wafer (either alone or in assemblies comprising other materials thereon), and semiconductive material layers (either alone or in assemblies comprising other materials). The term “substrate” refers to any supporting structure, including, but not limited to, the semiconductive substrates described above. Further in the context of this document, the term “layer” encompasses both the singular and the plural, unless otherwise indicated.
  • [0020]
    An insulative layer 14, for example silicon dioxide, is formed over substrate material 12. By way of example only, such depicts a substrate over which a capacitor will be fabricated. Any conceivable substrate is contemplated, whether existing or yet-to-be developed. A conductive metal first electrode layer 16 is formed over substrate 12/14. Such material is oxidizable at and above some oxidation temperature in the presence of an oxygen containing material to a higher degree at and above such temperature as compared to any degree of oxidation below such temperature. The oxidation temperature referred to is not necessarily the minimum temperature at which the material will oxidize in the presence of the oxygen containing material, for example as conditions in addition to temperature can effect whether a given material will oxidize. Rather, the stated oxidation temperature can be any temperature at which the material can oxidize in the presence of the oxygen containing material. Exemplary conductive metals include metal nitrides such as titanium nitride, tungsten nitride and tantalum nitride. These materials appreciably oxidize in the presence of many oxygen containing materials at an exemplary oxidation temperature of 300° C. and above. Electrode layer 16 might be formed by any existing or yet-to-be developed method, for example by sputtering, chemical vapor deposition and/or atomic layer deposition.
  • [0021]
    Referring to FIG. 2, at least one oxygen containing vapor precursor is fed to conductive first metal electrode layer 16 below the selected oxidation temperature under conditions effective to form a first portion oxide material 18 over conductive metal first electrode layer 16. Accordingly with the above exemplary materials, an exemplary preferred oxidation temperature below which the at least one vapor precursor is flowed is 300° C., by way of example only 290° C. First portion 18 will comprise a portion of a capacitor dielectric region 20, as will be apparent from the continuing discussion. By way of example only, an exemplary preferred material is aluminum oxide. Also as shown, first portion 18 is preferably formed “on” (meaning in direct physical contact with) conductive metal first electrode layer 16. Most preferably, first portion oxide material 18 is formed without any measurable oxidation occurring of metal first electrode layer 14, although some oxidation thereof is not precluded in the broadest considered aspects of the invention, as claimed. By way of example only, the conditions might include chemical vapor deposition (for example feeding multiple vapor precursors simultaneously to the substrate), atomic layer deposition, yet-to-be developed methods and/or any combination thereof. For example with respect to atomic layer deposition, the conditions might include previous formation of a monolayer to which one or more multiple oxygen containing precursor feeds occur.
  • [0022]
    Referring to FIG. 3, at least one vapor precursor is fed over first portion 18 at a temperature above the oxidation temperature effective to form a second portion oxide material 22 of capacitor dielectric region 20 over first portion 18. In one preferred embodiment, the precursor flowing during the formation of the second portion oxide material is at a temperature which is at least 25° C. higher than during the formation of the first portion oxide material, in another preferred embodiment at a temperature which is at least 50° C. higher, and in yet another preferred embodiment at a temperature which is at least 100° C. higher. Regardless, the oxide material of first portion 18 and second portion 22 are of the same/common chemical composition. However, the oxide of the second material might be of higher density and have superior electrical properties as compared to the first portion of the oxide material. The vapor precursor(s) used to form portion 22 might be the same or different from that/those used to form portion 18. Preferably and as shown, second portion 22 is formed on first portion 18. Preferably, second portion 22 is formed using the same general technique by which first portion 18 was formed, for example both by atomic layer deposition or both by chemical vapor deposition. Further preferably, first portion 18 and second portion 22 are formed in the same/common deposition chamber without removing the substrate from such chamber intermediate the formation of the first and second portions. In one preferred implementation, the second portion oxide material and the first portion oxide material are formed using at least the same pressure and same one or more precursors. In one preferred implementation, the second portion oxide material is formed using identical conditions (meaning at least the same pressure, precursors and flow rates) under which the first portion oxide material is formed, but for different temperature. Most preferably, first portion 18 restricts oxidation of the conductive metal first electrode layer during the formation of second portion 22. For example with respect aluminum oxide, the initial deposition of portion 18 at the lower temperature forms a less dense aluminum oxide than the aluminum oxide of portion 22 formed at the higher temperature, with portion 18 restricting oxidation of the underlying metal during formation of portion 22.
  • [0023]
    First and second portions 18, 22 might be formed to the same respective thickness, or to different thicknesses. Typically, and for example with respect to aluminum oxide, deposition of first portion 18 at temperatures below which significant oxidation would occur under typical deposition conditions and times results in a less than desired density layer (at least as initially deposited). Accordingly in one preferred embodiment, first portion 18 is formed to a thickness which is less than that of second portion 22, more preferably to a thickness which is no greater than one-third that of the second portion, and even more preferably to a thickness which is no greater than one-fifth that of the second portion.
  • [0024]
    Referring to FIG. 4, a conductive second electrode layer 24 has been formed over second portion oxide material 22, and preferably on such material as shown, of capacitor dielectric region 20. Preferred materials include conductive metal materials, for example the conductive metal nitrides referred to above. In one exemplary preferred embodiment, the entirety of the capacitor dielectric region 20 intermediate first electrode layer 14 and second electrode layer 24 consists essentially of aluminum oxide. Exemplary preferred thickness ranges for each of electrodes 16 and 24 include from 100 Angstroms to 200 Angstroms, with an exemplary thickness range for capacitor dielectric region 20 being from 40 Angstroms to 60 Angstroms.
  • [0025]
    By way of example only, exemplary capacitor dielectric materials include any one or combination of HfO2, Ta2O5, Y2O3, ZrO2, HfSiO4, ZrSiO4 and YSiO4. Further non-oxygen containing capacitor dielectric materials might be employed alternately or in addition to oxygen containing capacitor dielectric materials. Where an oxide is to be formed, exemplary oxidizers include O2, O3, H2O, NO2, NO and any alcohols (including polyols). Exemplary precursors include metallorganic precursors, for example tertbutylaluminum alkoxide, triethylaluminum, trimethylaluminum, tetrakisdimethylamido hafnium, pentathoxy tantalum, n!butyl cyclopentadienyl yttrium, and other metal alkyls or metal alkoxides.
  • [0026]
    While the above described embodiment shows the layers as being blanketly deposited, any partial deposition technique (whether existing or yet-to-be developed) is also of course contemplated. Further, the respective illustrated layers can patterned at any time into a desired shape of a capacitor if not deposited or otherwise initially formed in such shape.
  • [0027]
    By way of example only, an exemplary method of forming a capacitor using atomic layer deposition at least in part for the formation of a capacitor dielectric layer is described with reference to FIGS. 5-8 with respect to a substrate 10 a. Like numerals from the first described embodiment have been utilized where appropriate, with differences being indicated with the suffix “a” or with different numerals. Referring to FIG. 5, a conductive metal first electrode layer 16 has been formed over a substrate, with the conductive metal being oxidizable to a higher degree at and above an oxidation temperature as compared to any degree of oxidation below the oxidation temperature. Exemplary preferred materials are as described above with respect to the FIGS. 1-4 embodiment. A metal containing first species is chemisorbed to form a first species monolayer 30 from a gaseous first precursor onto conductive metal first electrode layer 16. In the illustrated example, an exemplary gaseous first precursor is trimethylaluminum forming a metal containing first species in the form of Al(CH3)x.
  • [0028]
    Referring to FIG. 6, at a temperature below the selected oxidation temperature of at least the outermost portion of material 16, the chemisorbed first species has been contacted with an oxygen containing gaseous second precursor to react with the first species and form a dielectric oxide monolayer 35 which comprises the metal of the first species, namely the aluminum as shown in the illustrated example. Exemplary oxygen containing gaseous second precursors are any of those oxidizers identified above. Of course, monolayers 30 and 35 as described above might be discontinuously formed with respect to their respective underlying substrates. Such discontinuous or less than saturated monolayers are, however, considered a monolayer in the context of this document. Further, multiple of the above-described chemisorbings and contactings might be repeated once or multiple times prior to further processing. Further, the above-described chemisorbing and contacting might be conducted at a common temperature or at different temperatures, and even under other different conditions. Further, inert gas flow might be included with or intermediate the respective chemisorbing and contacting, or the deposition chamber pumped down without any inert gas feed towards purging the respective gaseous precursors from the chamber.
  • [0029]
    Referring to FIG. 7, the metal containing first species is chemisorbed from the gaseous first precursor to form another first species monolayer 40 over the substrate which comprises the dielectric metal oxide.
  • [0030]
    Referring to FIG. 8, at a temperature above the oxidation temperature, the another first species monolayer 40 is contacted with an oxygen containing gaseous second precursor (i.e., the same or different as utilized above) to react with the first species and form another dielectric metal oxide monolayer 45 comprising the metal of the first species. During such formation, dielectric metal oxide monolayer 35 comprises a shield which, at least partially, restricts oxidation of conductive metal electrode layer 16 during such contacting of the another first species monolayer with the oxygen containing gaseous second precursor. As above, said monolayer 45 might be discontinuously formed/less than saturated such that the FIGS. 7 and 8 chemisorbing and contacting might be repeated at least once or multiple times more, prior to subsequent processing. Further as alluded to above, it might be desirable that the thickness of the sub-oxidation temperature material be greater than a saturated monolayer thick and, as well, be less than a total thickness of a second portion of the metal oxide layer being formed. Accordingly, the exemplary depicted chemisorbings and contactings exemplified by FIGS. 7 and 8 might be repeated more times than are the chemisorbings and contactings depicted by FIGS. 5 and 6, for example at least five times more, to achieve a corresponding thicker second portion as compared to the first portion. Also, the chemisorbing and contacting exemplified by the FIGS. 7 and 8 processings might be conducted at a common temperature or different temperatures.
  • [0031]
    A conductive second electrode layer would be formed over, and preferably on, the another dielectric metal oxide monolayer, typically as described above with respect with the first described embodiment.
  • [0032]
    By way of example only, for a material which has an oxidation temperature of around 300° C., the processing depicted by FIG. 6 would be conducted at a temperature no greater than 300° C., and the processing depicted by FIG. 8 would be conducted at a temperature of at least 325° C., and could of course be conducted at a higher temperature, for example of at least 425° C.
  • [0033]
    An exemplary preferred deposition range for the first portion formed with present generation processing is from about 5 Angstroms to about 20 Angstroms, with an exemplary thickness for the second portion being from about 10 Angstroms to about 40 Angstroms. An exemplary prior art atomic layer deposition method of forming an Al2O3 layer includes an aluminum precursor of trimethyl aluminum and an oxygen containing precursor of an O3 and O2 mixture containing from 5% to 20% by weight O3. Prior art depositions have occurred at temperatures above 300° C., with 460° C. being a specific example. Pressure typically ranges from 200 mTorr to 5 Torr, with 1 Torr being a specific example. The typical thickness of the aluminum oxide formed for the capacitor dielectric layer is about 50 Angstroms, with metal electrode material therebeneath forming undesirable quantities of oxides of the metal of the underlying electrode material.
  • [0034]
    In a reduction-to-practice example in accordance with an aspect of the invention, a first portion of the oxide material, as described above, was formed in six complete ALD cycles using the above precursors at 250° C. and a pressure of 1 Torr. The substrate was received within a chamber having a volume of from about 1 liter to 2 liters, and the precursor pulses lasted from 1 to 2 seconds, respectively, with intervening inert argon purge pulsings. Such resulted in an average thickness of a first portion as described above which was substantially continuous/saturated at about from 4 Angstroms to 5 Angstroms, resulting in a probably discontinuous average deposition thickness of about 0.8 Angstroms per cycle. This was followed under otherwise identical conditions but at an increased temperature of 450° C. for about 50 complete deposition cycles, which resulted in a 40 Angstrom thick second portion at the higher deposition temperature, and without noticeable oxidation of the underlying metal nitride electrode material.
  • [0035]
    In compliance with the statute, the invention has been described in language more or less specific as to structural and methodical features. It is to be understood, however, that the invention is not limited to the specific features shown and described, since the means wherein disclosed comprise preferred forms of putting the invention into effect. The invention is, therefore, claimed in any of its forms or modifications within the proper scope of the appended claims appropriately interpreted in accordance with the doctrine of equivalents.

Claims (34)

  1. 1. A method of forming a capacitor, comprising:
    forming a conductive metal nitride comprising first electrode layer over a substrate, the conductive metal nitride being oxidizable to a higher degree at and above an oxidation temperature of 300° C. as compared to any degree of oxidation below the oxidation temperature of 300° C.;
    feeding at least one oxygen containing vapor precursor to the conductive metal nitride comprising first electrode layer below the 300° C. oxidation temperature under conditions effective to form a first portion oxide material comprising aluminum oxide of a first density of a capacitor dielectric region over the conductive metal nitride comprising first electrode layer;
    feeding at least one oxygen containing vapor precursor over the first portion at a temperature above the 300° C. oxidation temperature effective to form a second portion oxide material comprising aluminum oxide of a second density of the capacitor dielectric region over the first portion, the oxide comprising material of the first portion and the oxide material of the second portion being common in chemical composition and the second density being greater than the first density; and
    forming a conductive second electrode layer over the second portion oxide material of the capacitor dielectric region.
  2. 2. The method of claim 1 wherein the first and second portions are formed from a common vapor precursor.
  3. 3. The method of claim 1 wherein the first and second portions are formed from different precursors.
  4. 4. The method of claim 1 wherein the first and second portions are formed by chemical vapor deposition.
  5. 5. The method of claim 1 wherein the first and second portions are formed by chemical vapor deposition using at least one common vapor precursor.
  6. 6. The method of claim 1 wherein the first and second portions are formed by chemical vapor deposition respectively comprising feeding multiple vapor precursors simultaneously to the substrate.
  7. 7. The method of claim 1 wherein the first and second portions are formed by chemical vapor deposition respectively comprising feeding common multiple vapor precursors simultaneously to the substrate.
  8. 8. The method of claim 1 wherein the first and second portions are formed by atomic layer deposition.
  9. 9. The method of claim 1 wherein the first portion is formed on the conductive metal nitride comprising first electrode layer.
  10. 10. The method of claim 1 wherein the second portion is formed on the first portion.
  11. 11. The method of claim 1 wherein the first portion is formed on the conductive metal nitride comprising first electrode layer, and the second portion is formed on the first portion.
  12. 12. (Canceled).
  13. 13. The method of claim 1 wherein the first portion is formed to a thickness which is less than that of the second portion.
  14. 14. The method of claim 1 wherein the first portion is formed to a thickness which is no greater than one-third that of the second portion.
  15. 15. The method of claim 1 wherein the first portion is formed to a thickness which is no greater than one-fifth that of the second portion.
  16. 16. (Canceled).
  17. 17. The method of claim 1 wherein the oxide material consists essentially of aluminum oxide, and an entirety of the capacitor dielectric region intermediate the first and second electrode layers consists essentially of aluminum oxide.
  18. 18. The method of claim 1 wherein the first portion oxide material is formed without any measurable oxidation occurring of the metal nitride comprising first electrode layer.
  19. 19. The method of claim 1 wherein the second portion oxide material and the first portion oxide material are formed using the same pressure and same one or more precursors.
  20. 20. The method of claim 1 wherein the second portion oxide material is formed using identical conditions under which the first portion oxide material is formed but for different temperature.
  21. 21. The method of claim 1 wherein the first and second portions are formed in a common deposition chamber without removing the substrate from such chamber intermediate formation of the first and second portions.
  22. 22. The method of claim 1 wherein the precursor flowing during formation of the second portion oxide material is at a temperature which is at least 25° C. higher than during formation of the first portion oxide material.
  23. 23. The method of claim 1 wherein the precursor flowing during formation of the second portion oxide material is at a temperature which is at least 50° C. higher than during formation of the first portion oxide material.
  24. 24. The method of claim 1 wherein the precursor flowing during formation of the second portion oxide material is at a temperature which is at least 100° C. higher than during formation of the first portion oxide material.
  25. 25-67. (Canceled).
  26. 68. The method of claim 1 wherein the first portion oxide material is formed at a temperature of about 290° C.
  27. 69. The method of claim 1 wherein the capacitor dielectric region is from 40 Angstroms to 60 Angstroms in thickness.
  28. 70. The method of claim 1 wherein formation of the first and second portions is blanketly over the substrate.
  29. 71. The method of claim 1 wherein formation of the first and second portions is only partially over the substrate.
  30. 72. The method of claim 1 wherein the oxygen containing vapor precursor in formation of at least one of the first and second oxide portions comprises at least one of O2, O3, H2O, NO2, NO and an alcohol.
  31. 73. The method of claim 72 wherein the oxygen containing vapor precursor in formation of at least one of the first and second oxide portions comprises an alcohol.
  32. 74. The method of claim 73 wherein the alcohol comprises a polyol.
  33. 75. The method of claim 1 wherein the first portion is formed by chemical vapor deposition and the second portion is formed by atomic layer deposition.
  34. 76. The method of claim 1 wherein the second portion is formed by chemical vapor deposition and the first portion is formed by atomic layer deposition.
US10636035 2003-08-06 2003-08-06 Methods of forming capacitors Expired - Fee Related US6855594B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US10636035 US6855594B1 (en) 2003-08-06 2003-08-06 Methods of forming capacitors

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US10636035 US6855594B1 (en) 2003-08-06 2003-08-06 Methods of forming capacitors
US10914824 US7056784B2 (en) 2003-08-06 2004-08-09 Methods of forming capacitors by ALD to prevent oxidation of the lower electrode
US11364383 US7759717B2 (en) 2003-08-06 2006-02-27 Capacitors comprising dielectric regions having first and second oxide material portions of the same chemical compositon but different densities

Publications (2)

Publication Number Publication Date
US20050032302A1 true true US20050032302A1 (en) 2005-02-10
US6855594B1 US6855594B1 (en) 2005-02-15

Family

ID=34116359

Family Applications (3)

Application Number Title Priority Date Filing Date
US10636035 Expired - Fee Related US6855594B1 (en) 2003-08-06 2003-08-06 Methods of forming capacitors
US10914824 Active US7056784B2 (en) 2003-08-06 2004-08-09 Methods of forming capacitors by ALD to prevent oxidation of the lower electrode
US11364383 Active US7759717B2 (en) 2003-08-06 2006-02-27 Capacitors comprising dielectric regions having first and second oxide material portions of the same chemical compositon but different densities

Family Applications After (2)

Application Number Title Priority Date Filing Date
US10914824 Active US7056784B2 (en) 2003-08-06 2004-08-09 Methods of forming capacitors by ALD to prevent oxidation of the lower electrode
US11364383 Active US7759717B2 (en) 2003-08-06 2006-02-27 Capacitors comprising dielectric regions having first and second oxide material portions of the same chemical compositon but different densities

Country Status (1)

Country Link
US (3) US6855594B1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060258085A1 (en) * 2004-07-20 2006-11-16 Derderian Garo J Methods of forming capacitors
US20080048225A1 (en) * 2006-08-25 2008-02-28 Micron Technology, Inc. Atomic layer deposited barium strontium titanium oxide films
US20150179730A1 (en) * 2013-12-19 2015-06-25 Intermolecular, Inc. ZrO-Based High K Dielectric Stack for Logic Decoupling Capacitor or Embedded DRAM

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7002790B2 (en) * 2002-09-30 2006-02-21 Medtronic, Inc. Capacitor in an implantable medical device
US7079377B2 (en) * 2002-09-30 2006-07-18 Joachim Hossick Schott Capacitor and method for producing a capacitor
US7183184B2 (en) * 2003-12-29 2007-02-27 Intel Corporation Method for making a semiconductor device that includes a metal gate electrode
US7491246B2 (en) * 2006-03-31 2009-02-17 Medtronic, Inc. Capacitor electrodes produced with atomic layer deposition for use in implantable medical devices
US7801623B2 (en) * 2006-06-29 2010-09-21 Medtronic, Inc. Implantable medical device having a conformal coating
US20080272421A1 (en) * 2007-05-02 2008-11-06 Micron Technology, Inc. Methods, constructions, and devices including tantalum oxide layers
US8012532B2 (en) 2007-12-18 2011-09-06 Micron Technology, Inc. Methods of making crystalline tantalum pentoxide
US8124528B2 (en) * 2008-04-10 2012-02-28 Micron Technology, Inc. Method for forming a ruthenium film
US8208241B2 (en) * 2008-06-04 2012-06-26 Micron Technology, Inc. Crystallographically orientated tantalum pentoxide and methods of making same
US8501268B2 (en) * 2010-03-09 2013-08-06 Micron Technology, Inc. Methods of forming material over a substrate and methods of forming capacitors

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5719417A (en) * 1996-11-27 1998-02-17 Advanced Technology Materials, Inc. Ferroelectric integrated circuit structure
US5783253A (en) * 1996-09-07 1998-07-21 Lg Semicon Co., Ltd. Method for forming a dielectric film and method for fabricating a capacitor using the same
US6207522B1 (en) * 1998-11-23 2001-03-27 Microcoating Technologies Formation of thin film capacitors
US6218233B1 (en) * 1997-11-04 2001-04-17 Nec Corporation Thin film capacitor having an improved bottom electrode and method of forming the same
US6245606B1 (en) * 1998-11-17 2001-06-12 Texas Instruments Incorporated Low temperature method for forming a thin, uniform layer of aluminum oxide
US6265259B1 (en) * 1998-02-06 2001-07-24 Texas Instruments-Acer Incorporated Method to fabricate deep sub-μm CMOSFETs
US6355519B1 (en) * 1998-12-30 2002-03-12 Hyundai Electronics Industries Co., Ltd. Method for fabricating capacitor of semiconductor device
US6358789B2 (en) * 1999-12-24 2002-03-19 Hyundai Electronics Industries Co., Ltd. Method for manufacturing a semiconductor device having a capacitor
US20020086556A1 (en) * 2001-01-04 2002-07-04 Ahn Kie Y. Methods of forming silicon-doped aluminum oxide, and methods of forming transistors and memory devices
US20020135048A1 (en) * 2001-02-23 2002-09-26 Micron Technology, Inc. Doped aluminum oxide dielectrics
US6469333B1 (en) * 1999-07-29 2002-10-22 Fujitsu Limited Semiconductor device having a ferroelectric film and a fabrication process thereof
US6743475B2 (en) * 2000-10-23 2004-06-01 Asm International N.V. Process for producing aluminum oxide films at low temperatures
US6777776B2 (en) * 2002-10-28 2004-08-17 Kabushiki Kaisha Toshiba Semiconductor device that includes a plurality of capacitors having different capacities

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR930012120B1 (en) * 1991-07-03 1993-12-24 김광호 Semicondcutor device and fabricating method thereof
US6730559B2 (en) * 1998-04-10 2004-05-04 Micron Technology, Inc. Capacitors and methods of forming capacitors
JP3943294B2 (en) * 1999-08-18 2007-07-11 株式会社ルネサステクノロジ The semiconductor integrated circuit device
US6342445B1 (en) * 2000-05-15 2002-01-29 Micron Technology, Inc. Method for fabricating an SrRuO3 film
JP2002064184A (en) * 2000-06-09 2002-02-28 Oki Electric Ind Co Ltd Manufacturing method of semiconductor device comprising capacitor part
KR100385952B1 (en) * 2001-01-19 2003-06-02 삼성전자주식회사 A semiconductor capacitor having tantalum oxide as dielctric film and formation method thereof
US6818553B1 (en) * 2002-05-15 2004-11-16 Taiwan Semiconductor Manufacturing Company, Ltd. Etching process for high-k gate dielectrics
KR100480622B1 (en) * 2002-10-16 2005-03-31 삼성전자주식회사 Semiconductor device having dielectric layer improved dielectric characteristic and leakage current and method for manufacturing the same
KR100536030B1 (en) * 2003-02-25 2005-12-12 삼성전자주식회사 Method for forming a capacitor in a semiconductor device
KR100988081B1 (en) * 2003-04-23 2010-10-18 삼성전자주식회사 Magnetic Random Access Memory comprising middle oxide layer formed with hetero-method and method of manufacturing the same
JP5032145B2 (en) * 2006-04-14 2012-09-26 株式会社東芝 Semiconductor device

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5783253A (en) * 1996-09-07 1998-07-21 Lg Semicon Co., Ltd. Method for forming a dielectric film and method for fabricating a capacitor using the same
US5719417A (en) * 1996-11-27 1998-02-17 Advanced Technology Materials, Inc. Ferroelectric integrated circuit structure
US6218233B1 (en) * 1997-11-04 2001-04-17 Nec Corporation Thin film capacitor having an improved bottom electrode and method of forming the same
US6265259B1 (en) * 1998-02-06 2001-07-24 Texas Instruments-Acer Incorporated Method to fabricate deep sub-μm CMOSFETs
US6245606B1 (en) * 1998-11-17 2001-06-12 Texas Instruments Incorporated Low temperature method for forming a thin, uniform layer of aluminum oxide
US6207522B1 (en) * 1998-11-23 2001-03-27 Microcoating Technologies Formation of thin film capacitors
US6355519B1 (en) * 1998-12-30 2002-03-12 Hyundai Electronics Industries Co., Ltd. Method for fabricating capacitor of semiconductor device
US6469333B1 (en) * 1999-07-29 2002-10-22 Fujitsu Limited Semiconductor device having a ferroelectric film and a fabrication process thereof
US6358789B2 (en) * 1999-12-24 2002-03-19 Hyundai Electronics Industries Co., Ltd. Method for manufacturing a semiconductor device having a capacitor
US6743475B2 (en) * 2000-10-23 2004-06-01 Asm International N.V. Process for producing aluminum oxide films at low temperatures
US20020086556A1 (en) * 2001-01-04 2002-07-04 Ahn Kie Y. Methods of forming silicon-doped aluminum oxide, and methods of forming transistors and memory devices
US20020135048A1 (en) * 2001-02-23 2002-09-26 Micron Technology, Inc. Doped aluminum oxide dielectrics
US6777776B2 (en) * 2002-10-28 2004-08-17 Kabushiki Kaisha Toshiba Semiconductor device that includes a plurality of capacitors having different capacities

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060258085A1 (en) * 2004-07-20 2006-11-16 Derderian Garo J Methods of forming capacitors
US7465627B2 (en) * 2004-07-20 2008-12-16 Micron Technology, Inc. Methods of forming capacitors
US20080048225A1 (en) * 2006-08-25 2008-02-28 Micron Technology, Inc. Atomic layer deposited barium strontium titanium oxide films
US20090315089A1 (en) * 2006-08-25 2009-12-24 Ahn Kie Y Atomic layer deposited barium strontium titanium oxide films
US8581352B2 (en) 2006-08-25 2013-11-12 Micron Technology, Inc. Electronic devices including barium strontium titanium oxide films
US9202686B2 (en) 2006-08-25 2015-12-01 Micron Technology, Inc. Electronic devices including barium strontium titanium oxide films
US20150179730A1 (en) * 2013-12-19 2015-06-25 Intermolecular, Inc. ZrO-Based High K Dielectric Stack for Logic Decoupling Capacitor or Embedded DRAM
US9099430B2 (en) * 2013-12-19 2015-08-04 Intermolecular, Inc. ZrO-based high K dielectric stack for logic decoupling capacitor or embedded DRAM

Also Published As

Publication number Publication date Type
US7056784B2 (en) 2006-06-06 grant
US7759717B2 (en) 2010-07-20 grant
US20050032325A1 (en) 2005-02-10 application
US6855594B1 (en) 2005-02-15 grant
US20060145294A1 (en) 2006-07-06 application

Similar Documents

Publication Publication Date Title
US6596583B2 (en) Methods for forming and integrated circuit structures containing ruthenium and tungsten containing layers
US6800567B2 (en) Method for forming polyatomic layers
US7666773B2 (en) Selective deposition of noble metal thin films
US6165834A (en) Method of forming capacitors, method of processing dielectric layers, method of forming a DRAM cell
US6429127B1 (en) Methods for forming rough ruthenium-containing layers and structures/methods using same
US20040018747A1 (en) Deposition method of a dielectric layer
US20030042526A1 (en) Method of improved high K dielectric-polysilicon interface for CMOS devices
US6825129B2 (en) Method for manufacturing memory device
US20030049942A1 (en) Low temperature gate stack
US6162744A (en) Method of forming capacitors having high-K oxygen containing capacitor dielectric layers, method of processing high-K oxygen containing dielectric layers, method of forming a DRAM cell having having high-K oxygen containing capacitor dielectric layers
US6297539B1 (en) Doped zirconia, or zirconia-like, dielectric film transistor structure and deposition method for same
US6989573B2 (en) Lanthanide oxide/zirconium oxide atomic layer deposited nanolaminate gate dielectrics
US20030234417A1 (en) Dielectric layers and methods of forming the same
US20040141390A1 (en) Capacitor of semiconductor device and method for manufacturing the same
US6319832B1 (en) Methods of making semiconductor devices
EP1124262A2 (en) Multilayer dielectric stack and method
US20060263977A1 (en) Methods of forming integrated circuit electrodes and capacitors by wrinkling a layer that includes a high percentage of impurities
US6509280B2 (en) Method for forming a dielectric layer of a semiconductor device
US6849505B2 (en) Semiconductor device and method for fabricating the same
US6844604B2 (en) Dielectric layer for semiconductor device and method of manufacturing the same
US20040033661A1 (en) Semiconductor device and method for manufacturing the same
US20050208718A1 (en) Methods of forming a capacitor using an atomic layer deposition process
US20090148625A1 (en) Method for forming thin film
US20050042373A1 (en) Atomic layer deposition methods of forming conductive metal nitride comprising layers
US20030017266A1 (en) Chemical vapor deposition methods of forming barium strontium titanate comprising dielectric layers, including such layers having a varied concentration of barium and strontium within the layer

Legal Events

Date Code Title Description
AS Assignment

Owner name: MICRON TECHNOLOGY, INC., IDAHO

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:BHAT, VISHWANATH;CARLSON, CHRIS M.;GEALY, F. DANIEL;REEL/FRAME:014385/0607;SIGNING DATES FROM 20030724 TO 20030731

CC Certificate of correction
FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

AS Assignment

Owner name: U.S. BANK NATIONAL ASSOCIATION, AS COLLATERAL AGEN

Free format text: SECURITY INTEREST;ASSIGNOR:MICRON TECHNOLOGY, INC.;REEL/FRAME:038669/0001

Effective date: 20160426

AS Assignment

Owner name: MORGAN STANLEY SENIOR FUNDING, INC., AS COLLATERAL

Free format text: PATENT SECURITY AGREEMENT;ASSIGNOR:MICRON TECHNOLOGY, INC.;REEL/FRAME:038954/0001

Effective date: 20160426

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Expired due to failure to pay maintenance fee

Effective date: 20170215

AS Assignment

Owner name: U.S. BANK NATIONAL ASSOCIATION, AS COLLATERAL AGEN

Free format text: CORRECTIVE ASSIGNMENT TO CORRECT THE REPLACE ERRONEOUSLY FILED PATENT #7358718 WITH THE CORRECT PATENT #7358178 PREVIOUSLY RECORDED ON REEL 038669 FRAME 0001. ASSIGNOR(S) HEREBY CONFIRMS THE SECURITY INTEREST;ASSIGNOR:MICRON TECHNOLOGY, INC.;REEL/FRAME:043079/0001

Effective date: 20160426